Fabrication process of a semiconductor integrated circuit device

ABSTRACT

With a view to preventing the oxidation of a metal film at the time of light oxidation treatment after gate patterning and at the same time to making it possible to control the reproducibility of oxide film formation and homogeneity of oxide film thickness at gate side-wall end portions, in a gate processing step using a poly-metal, a gate electrode is formed by patterning a gate electrode material which has been deposited over a semiconductor wafer  1 A having a gate oxide film formed thereon and has a poly-metal structure and then, the principal surface of the semiconductor wafer  1 A heated to a predetermined temperature or vicinity thereof is supplied with a hydrogen gas which contains water at a low concentration, the water having been formed from hydrogen and oxygen by a catalytic action, to selectively oxidize the principal surface of the semiconductor wafer  1 A, whereby the profile of the side-wall end portions of the gate electrode is improved.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to a process for the fabrication of asemiconductor integrated circuit device, particularly to a techniqueeffective when applied to gate processing of MOSFET (Metal OxideSemiconductor Field Effect Transistor) having a poly-metal gate.

[0003] 2. Description of the Related Art

[0004] In Japanese Patent Application Laid-Open No. H5-152282 (whichwill hereinafter be called “Ohmi”), disclosed is an oxide film formingdevice for oxidizing a semiconductor wafer or the like with watersynthesized using a catalyst such as nickel.

[0005] In pages 128-133 of Papers of the Lecture addressed at the 45-thSymposium of Semiconductor Integrated Circuit Technique held on Dec.1-2, 1992 (which will hereinafter be called “Nakamura”) , disclosed isoxide film formation under a strong reducing atmosphere which containswater vapor synthesized by a stainless catalyst.

[0006] In Japanese Patent Application Laid-Open No. S59-132136 (whichwill hereinafter be called “Kobayashi”)), disclosed is a process, in asilicon semiconductor integrated circuit device having a refractorymetal (high-melting point metal) gate, for carrying out auxiliarythermal oxidation (which will hereinafter be called “light oxidation” or“auxiliary oxidation after gate formation”) of not a gate metal itselfbut necessary portions other than the gate metal under a mixedatmosphere of water vapor and hydrogen after gate patterning, therebyadjusting an insulation film at the periphery below the gate.

[0007] Similarly, in Japanese Patent Application Laid-Open No. H3-119763(which will hereinafter be called “Katada”) and Japanese PatentApplication Laid-Open No. H7-94716 (which will hereinafter be called“Muraoka”), disclosed is a process for forming a gate having athree-layered structure made of tungsten, titanium nitride andpolysilicon and then subjecting it to oxidation treatment under a mixedatmosphere of hydrogen, water vapor and nitrogen.

[0008] It is presumed that for a device having a circuit formed of aminute MOSFET whose gate length is 0.25 μm or smaller, such as DRAM(Dynamic Random Access Memory) available since the development of 256Mbit (megabit), a gate processing step using a low-resistance conductivematerial including a metal film will become indispensable to reduce aparasitic resistance of a gate electrode.

[0009] As such a low-resistance gate electrode material, so-calledpoly-metal (which generally means a refractory metal formed directly orindirectly over a polycrystalline silicon electrode) having a refractorymetal film stacked over a polycrystalline silicon film is regarded aspromising. The poly-metal can be used not only as a gate electrodematerial but also as an interconnection material because of a sheetresistance as low as 2 Ω/□. According to the investigation by thepresent inventors, W (tungsten), Mo (molybdenum), Ti (titanium) or thelike which exhibits good low resistance even in the low temperatureprocess not higher than 800° C. and has high electro-migrationresistance is used as the refractory metal. Since the stacking of such arefractory metal film directly on a polycrystalline silicon film lowersthe adhesion between these two films or happens to form ahigh-resistance silicide layer at the interface between these two filmsby a high-temperature heat treatment process, the poly-metal gate ispractically formed of a three-layered structure having, between thepolycrystalline silicon film and the refractory metal film, a barrierlayer made of a metal nitride film such as TiN (titanium nitride) or WN(tungsten nitride).

[0010] Based on the investigation by the present inventors, gateprocessing is conventionally carried out as follows. First, asemiconductor substrate is thermally oxidized to form agate oxide filmon its surface. Although a thermally oxidized film is generally formedin a dry oxygen atmosphere, wet oxidation is employed for the formationof a gate oxide film because a defect density in the film can bereduced. In wet oxidation, a pyrogenic method is employed in which wateris formed by the combustion of hydrogen in an oxygen atmosphere and thenfed to the surface of a semiconductor wafer together with oxygen.

[0011] The pyrogenic method, however, is accompanied with the drawbackthat combustion is effected by igniting hydrogen jetted from a nozzleattached to the tip of a quartz-made hydrogen gas inlet tube, but heatgenerated upon combustion melts the nozzle and generates particles,which presumably become a contamination source of a semiconductor wafer.For the formation of water, therefore, a method using a catalyst withoutcombustion is also proposed.

[0012] The above-described Ohmi discloses a thermal oxidation apparatushaving a hydrogen gas inlet tube formed at its inside from Ni (nickel)or a Ni-containing material and being equipped with means for heatingthe hydrogen gas inlet tube. In this thermal oxidation apparatus, Ni (orNi-containing material) inside of the hydrogen gas inlet tube heated at300° C. or higher is brought into contact with hydrogen to generate ahydrogen activated species and then, the hydrogen activated species isreacted with oxygen (or an oxygen-containing gas), whereby water isgenerated. Water is thus generated in such a catalytic manner withoutcombustion so that neither melting of the quartz-made hydrogen gas inlettube at its tip point nor generation of particles occurs.

[0013] Over the gate oxide film formed by such wet oxidation method, agate electrode material is deposited, followed by patterning the gateelectrode material by dry etching with a photoresist as a mask. Afterthe photoresist is removed by ashing treatment, the dry etching residueor ashing residue on the surface of the substrate is removed using anetching solution such as hydrofluoric acid

[0014] By the above-described wet etching, the gate oxide film in aregion other than that below the gate electrode is etched and at thesame time, the gate oxide film at the side wall end portions of the gateelectrode are etched isotropically and undercuts are formed, whichbrings about inconveniences such as lowering in pressure resistance ofthe gate electrode. With a view to improving the profile havingundercuts formed at the side-wall end portions of the gate electrode,the substrate is subjected to light oxidation treatment, that is,thermal oxidation again to form an oxide film on its surface

[0015] The above-described refractory metals such as W and Mo areconsiderably prone to oxidation under a high-temperature oxygenatmosphere so that the application of the above light oxidationtreatment to a gate electrode of a poly-metal structure oxidizes therefractory metal film, thereby increasing its resistance or partiallypeeling off the film from the substrate. In the gate processing by usinga poly-metal, it is therefore necessary to take countermeasures againstthe oxidation of a refractory metal film upon light oxidation treatment.

[0016] The above-described Kobayashi discloses a technique ofselectively oxidizing Si without oxidizing a W (Mo) film by forming overa Si (silicon) substrate a gate electrode of a W- or Mo-film-containingpoly-metal structure and then carrying out light oxidation in a mixedatmosphere of water vapor and hydrogen. This technique makes use of thedifference between W (or Mo) and Si in a water vapor/hydrogen partialpressure ratio which brings about equilibrium in redox reaction. In thistechnique, selective oxidation of Si is realized by setting the partialpressure ratio within a range that W (or Mo) once oxidized by watervapor is reduced rapidly by coexisting hydrogen but Si remains oxidized.The mixed atmosphere of water vapor and hydrogen is generated by thebubbling system which feeds a hydrogen gas in pure water filled in acontainer and the water vapor/hydrogen partial pressure ratio iscontrolled by changing the temperature of the pure water.

[0017] The above-described Katada and Muraoka disclose a technique offorming a gate electrode of a poly-metal structure, more specifically,forming a metal nitride film such as TiN and a metal film such as W on aSi substrate through a gate oxide film, and then carrying out lightoxidation in an atmosphere obtained by diluting a reducing gas(hydrogen) and an oxidizing gas (water vapor) with nitrogen. Accordingto them, only Si can be oxidized selectively without oxidation of themetal film. At the same time, oxidation of the metal nitride film can beprevented, because denitrifying reaction from the nitride metal film canbe prevented by diluting the water vapor/hydrogen mixed gas withnitrogen.

[0018] As described above, in the step for forming a gate electrode of apoly-metal structure, it is effective for an improvement in the pressureresistance of a gate oxide film and oxidation prevention of a metalfilm, to carry out light oxidation in a water vapor/hydrogen mixed gashaving a predetermined partial pressure.

[0019] The conventional bubbling method which has been proposed as amethod for forming the water vapor/hydrogen mixed gas is accompaniedwith the drawback that since the water vapor/hydrogen mixed gas isgenerated by supplying a hydrogen gas into pure water charged in advancein a container, foreign matters mixed in pure water are fed to anoxidizing furnace together with the water vapor/hydrogen mixed gas andpresumably contaminates the semiconductor wafer.

[0020] The bubbling method is also accompanied with other drawbacks thatsince the water vapor/hydrogen partial pressure is controlled bychanging the temperature of pure water, (1) the partial pressure ratiovaries easily and the optimum pressure ratio cannot be attained withhigh precision, (2) the water vapor concentration on the order of ppmcannot be attained owing to the controllable range of the water vaporconcentration as narrow as several to ten-odd %.

[0021] As will be described later, in the redox reaction of Si or ametal by using a water vapor/hydrogen mixed gas, oxidation tends toproceed faster when the water vapor concentration is higher. When Si isoxidized at a comparatively high water vapor concentration as the watervapor/hydrogen mixed gas formed by the bubbling system, the oxide filmgrows in a markedly short time owing to a high oxidation rate. A minuteMOSFET having a gate length not greater than 0.25 μm is required to havea gate oxide film as thin as 5 nm or less in order to maintain theelectrical properties of the device. Accordingly, it is difficult toform such a ultra-thin gate oxide film uniformly and with goodcontrollability if the water vapor/hydrogen mixed gas generated by thebubbling method is used. When oxidation is carried out at a lowtemperature (for example, 80° C. or lower) to reduce the growth rate ofthe oxide film, a gate oxide film having good quality cannot beobtained.

SUMMARY OF THE INVENTION

[0022] An object of the present invention is to provide a techniquewhich prevents, in gate processing by using a poly-metal, the oxidationof a metal film upon light oxidation treatment after patterning of agate electrode and makes it possible to control reproducibility of theoxide film formation and homogeneity of the oxide film thickness at sidewall end portions of the gate electrode.

[0023] The above and other objects and novel features of the presentinvention will become apparent from the following description thereinand accompanying drawings.

[0024] Among the inventions disclosed in the present application,typical ones will be summarized briefly as follows:

[0025] (1) A process for the fabrication of a semiconductor integratedcircuit device according to the present invention comprises depositing aconductive film including at least a metal film over a gate oxide filmformed on the principal surface of a semiconductor substrate andpatterning the conductive film to form a gate electrode for MOSFET; andfeeding a hydrogen gas containing water vapor generated from hydrogenand oxygen by catalytic action to the principal surface of thesemiconductor substrate heated to a predetermined temperature orvicinity thereof to selectively oxidize the principal surface of thesemiconductor substrate, thereby improving a profile of side-wall endportions of the gate electrode.

[0026] (2) In the above process, the conductive film includes at least aW film or a Ti film.

[0027] (3) In the above process, a water vapor/hydrogen partial pressureratio of the water-vapor-containing hydrogen gas is set within a rangereducing the metal film and oxidizing the principal surface of thesemiconductor substrate.

[0028] (4) In the above process, the conductive film contains at least aTi film and the principal surface of the semiconductor substrate isselectively oxidized using a hydrogen gas which contains water vapor ata concentration low enough to suppress deterioration of the gateelectrode due to oxidation of the Ti film to the minimum.

[0029] (5) In the above process, the conductive film includes at least aW film and the principal surface of the semiconductor substrate isselectively oxidized using a hydrogen gas which contains water vapor ata concentration low enough to permit the control of an oxidation rateand oxide film thickness.

[0030] (6) A process for the fabrication of a semiconductor integratedcircuit device according to the present invention comprises depositing aconductive film including at least a metal film over a gate oxide film,which has been formed on the principal surface of a semiconductorsubstrate to have a film thickness not greater than 5 nm, and patterningthe conductive film to form a gate electrode for MOSFET; and feeding ahydrogen gas containing water vapor, which has been formed from hydrogenand oxygen by catalytic action, at a concentration low enough to permitthe control of reproducibility of oxide film formation and homogeneityof an oxide film thickness to the principal surface of the semiconductorsubstrate heated to a predetermined temperature or vicinity thereof toselectively oxidize the principal surface of the semiconductorsubstrate, thereby improving a profile of side-wall end portions of thegate electrode.

[0031] (7) A process for the fabrication of a semiconductor integratedcircuit device according to the present invention comprises followingsteps (a) to (d):

[0032] (a) thermally oxidizing a semiconductor substrate to form overthe principal surface thereof a gate oxide film and then depositing aconductive film containing at least a metal film over the gate oxidefilm;

[0033] (b) patterning the conductive film by dry etching with aphotoresist film as a mask to form a gate electrode for MOSFET;

[0034] (c) wet etching the principal surface of the semiconductorsubstrate after removal of the photoresist film; and

[0035] (d) setting a water vapor/hydrogen partial pressure ratio of ahydrogen gas containing water vapor generated from hydrogen and oxygenby catalytic action within a range which reduces the metal film andoxidizes the principal surface of the semiconductor substrate andselectively oxidizing the principal surface of the semiconductorsubstrate by feeding the water-vapor-containing hydrogen gas to theprincipal surface of the semiconductor substrate heated to apredetermined temperature or vicinity thereof, thereby improving aprofile of side-wall end portions of the gate electrode impaired by thewet etching.

[0036] (8) In the above process, the conductive film is made of apolycrystalline silicon film, a metal nitride film deposited over thepolycrystalline silicon film and a metal film deposited over the metalnitride film.

[0037] (9) In the above process, the metal nitride film is made of WN orTiN, while the metal film is made of W, Mo or Ti.

[0038] (10) In the above process, the gate electrode has a gate lengthnot greater than 0-25 μm.

[0039] (11) In the above process, the gate electrode is a gate electrodeof MISFET for memory cell selection which constitutes a memory cell ofDRAM.

[0040] (12) In the above process, the semiconductor substrate is heatedat 800 to 900° C.

[0041] (13) In the above process, the principal surface of thesemiconductor substrate is selectively oxidized by asingle-wafer-process system.

[0042] (14) In the above process, the principal surface of thesemiconductor substrate is selectively oxidized by batch treatment.

[0043] Other summaries of the present invention will next be describedby the item:

[0044] 1. A process for the fabrication of a semiconductor integratedcircuit device comprising the following steps:

[0045] (a) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0046] (b) forming a refractory metal film made mainly of tungsten overthe polysilicon film directly or through a barrier layer;

[0047] (c) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0048] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to additional thermal oxidation treatment under amixed atmosphere containing a hydrogen gas and water vapor synthesizedfrom oxygen and hydrogen gases by a catalyst.

[0049] 2. A process as described under item 1 above, wherein the barrierlayer contains a tungsten nitride film

[0050] 3. A process as described under item 2 above, wherein the step(d) is carried out under the conditions which do not substantiallyoxidize the refractory metal film and the barrier layer.

[0051] 4. A process as described under item 3 above, wherein the gateinsulation film contains a silicon oxide nitride film.

[0052] 5. A process for the preparation of a semiconductor integratedcircuit device, which comprises the following steps:

[0053] (a) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0054] (b) forming a refractory metal film over the polysilicon filmdirectly or through a barrier layer;

[0055] (c) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0056] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to additional thermal oxidation treatment under amixed atmosphere containing a hydrogen gas and water vapor synthesizedfrom oxygen and hydrogen gases by a catalyst.

[0057] 6. A process as described under item 5 above, wherein the barrierlayer is contained.

[0058] 7. A process as described under item 6 above, wherein the step(d) is carried out under the conditions which do not substantiallyoxidize the refractory metal film and the barrier layer.

[0059] 8. A process for the fabrication of a semiconductor integratedcircuit device, which comprises the following step:

[0060] (a) carrying out heat treatment to oxidize, between a firstregion and a second region being made of a material different from thatof the first region, each over a semiconductor wafer, the first regionunder a mixed atmosphere containing a hydrogen gas and water vaporsynthesized from oxygen and hydrogen gases by a catalyst withoutsubstantially oxidizing the second region.

[0061] 9. A process as described under item 8 above, wherein the firstregion is a part of the wafer itself.

[0062] 10. A process as described under item 9 above, wherein the secondregion is a thin film formed directly or indirectly over the surface ofthe wafer.

[0063] 11. A process for the fabrication of a semiconductor integratedcircuit device, which comprises following steps:

[0064] (a) forming a first film made mainly of silicon over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0065] (b) forming a refractory metal film over the polysilicon filmdirectly or through a barrier layer;

[0066] (c) forming a gate electrode by patterning the first film and therefractory metal film; and

[0067] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to additional thermal oxidation treatment under amixed atmosphere containing a hydrogen gas and water vapor synthesizedfrom oxygen and hydrogen gases by a catalyst.

[0068] 12. A process as described under item 11 above, wherein the step(d) is carried out under the conditions not substantially oxidizing therefractory metal film.

[0069] 13. A process for the fabrication of a semiconductor integratedcircuit device, which comprises the following steps:

[0070] (a) forming, on the silicon surface of a semiconductor wafer, agroove for element isolation,

[0071] (b) embedding the groove for element isolation with an embeddingmaterial from outside,

[0072] (c) flattening the surface of the wafer by chemical mechanicalpolishing subsequent to the step (b),

[0073] (d) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of the semiconductor wafer;

[0074] (e) forming a refractory metal film over the polysilicon filmdirectly or through a barrier layer;

[0075] (f) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0076] (g) subsequent to the step (f), subjecting the silicon andpolysilicon portions to thermal oxidation treatment withoutsubstantially oxidizing the refractory metal film under a mixedatmosphere containing a hydrogen gas and water vapor.

[0077] 14. A process as described under item 13 above, wherein thebarrier layer contains a nitride film of the refractory metal.

[0078] 15. A process as described under item 14 above, wherein therefractory metal is tungsten.

[0079] 16. A process for the fabrication of a CMOS semiconductorintegrated circuit device, which comprises the following steps:

[0080] (a) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0081] (b) forming a refractory metal film made mainly of tungsten overthe polysilicon film directly or through a barrier layer containing atungsten nitride film;

[0082] (c) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0083] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to thermal oxidation treatment withoutsubstantially oxidizing the refractory metal film under a mixedatmosphere containing a hydrogen gas and water vapor.

[0084] 17. A process for the fabrication of a CMOS semiconductorintegrated circuit device, which comprises the following steps:

[0085] (a) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0086] (b) forming a refractory metal film made mainly of tungsten overthe polysilicon film through a barrier layer containing a tungstennitride film;

[0087] (c) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0088] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to thermal oxidation treatment withoutsubstantially oxidizing the refractory metal film under a mixedatmosphere of gases oxidative and reductive to silicon and polysilicon.

[0089] 18. A process for the fabrication of a semiconductor integratedcircuit device, which comprises the following steps:

[0090] (a) forming a polysilicon film over asilicon-oxide-film-containing gate insulation film formed over thesilicon surface of a semiconductor wafer;

[0091] (b) forming a refractory metal film made mainly of tungsten overthe polysilicon film directly or through a barrier layer;

[0092] (c) forming a gate electrode by patterning the polysilicon filmand the refractory metal film; and

[0093] (d) subsequent to the step (c), subjecting the silicon andpolysilicon portions to additional thermal oxidation treatment withoutsubstantially oxidizing the refractory metal film under a mixedatmosphere of a gas reductive to silicon and polysilicon and anoxidizing gas synthesized by a catalyst oxidative to silicon andpolysilicon.

[0094] 19. A process as described under item 18 above, wherein thebarrier layer contains a tungsten nitride film.

[0095] 20. A process as described under item 19 above, wherein the gateinsulation film contains a silicon oxide nitride film.

[0096] Other summaries of the present invention will next be describedby the item as follows.

[0097] 21. A process for the fabrication of a semiconductor integratedcircuit, which comprises depositing a conductive film containing atleast a metal film over a gate oxide film formed on the principalsurface of a semiconductor substrate and then forming a gate electrodefor MOSFET by patterning the conductive film; and supplying a hydrogengas containing water vapor formed from hydrogen and oxygen by catalyticaction to the principal surface of the semiconductor substrate heated ata predetermined temperature or vicinity thereof and selectivelyoxidizing the principal surface of the semiconductor substrate, therebyimproving a profile of side-wall end portions of the gate electrode.

[0098] 22. A process as described under item 21 above, wherein theconductive film contains at least a W film or Ti film.

[0099] 23. A process as described under item 21 above, wherein a watervapor/hydrogen partial pressure ratio of the water-vapor-containinghydrogen gas is set within a range which reduces the metal film andoxidizes the principal surface of the semiconductor substrate.

[0100] 24. A process as described under item 21 above, wherein theconductive film contains at least a Ti film and the principal surface ofthe semiconductor substrate is selectively oxidized using a hydrogen gaswhich contains water vapor at a concentration low enough to suppressdeterioration of the gate electrode owing to the oxidation of the Tifilm to the minimum.

[0101] 25. A process as described under item 21 above, wherein theconductive film contains at least a W film and the principal surface ofthe semiconductor substrate is selectively oxidized using a hydrogen gaswhich contains water vapor at a concentration low enough to permit thecontrol of an oxidizing rate and oxide film thickness.

[0102] 26. A process for the fabrication of a semiconductor circuitdevice, which comprises depositing a conductive film containing at leasta metal film over a gate oxide film which has been formed on theprincipal surface of a semiconductor substrate to have a film thicknessnot greater than 5 nm and then forming a gate electrode for MOSFET bypatterning the conductive film; and supplying a hydrogen gas whichcontains water vapor, formed from hydrogen and oxygen by catalyticaction, at a concentration low enough to permit the control ofreproducibility of oxide film formation and homogeneity of oxide filmthickness to the principal surface of the substrate heated at apredetermined temperature or vicinity thereof and selectively oxidizingthe principal surface of the semiconductor substrate, thereby improvinga profile of side-wall end portions of the gate electrode.

[0103] 27. A process for the fabrication of a semiconductor integratedcircuit, which comprises the following steps (a) to (d):

[0104] (a) thermally oxidizing a semiconductor substrate to form a gateoxide film on the principal surface of the substrate and then depositinga conductive film containing at least a metal film over the gate oxidefilm;

[0105] (b) patterning the conductive film by dry etching with aphotoresist film as a mask, thereby forming a gate electrode for MOSFET;

[0106] (c) removing the photoresist film and then wet etching theprincipal surface of the semiconductor substrate; and

[0107] (d) setting a water vapor/hydrogen partial pressure ratio of ahydrogen gas containing water vapor generated from hydrogen and oxygenby catalytic action within a range which reduces the metal film andoxidizes the principal surface of the semiconductor substrate andselectively oxidizing the principal surface of the semiconductorsubstrate by feeding the water-vapor-containing hydrogen gas to theprincipal surface of the semiconductor substrate heated at apredetermined temperature or vicinity thereof, thereby improving theprofile of side-wall end portions of the gate electrode impaired by thewet etching.

[0108] 28. A process as described under item 27 above, wherein theconductive film is made of a polycrystalline silicon film, a metalnitride film deposited over the polycrystalline silicon film, and ametal film deposited over the metal nitride film.

[0109] 29. A process as described under item 28 above, wherein the metalnitride film is made of WN or TiN, while the metal film is made of W, Moor Ti.

[0110] 30. A process as described under item 27 above, wherein the gateelectrode has a gate length not greater than 0.25 μm.

[0111] 31. A process as described under item 27 above, wherein the gateelectrode is a gate electrode of MISFET for the memory cell selectionwhich constitutes a memory cell of DRAM.

[0112] 32. A process as described under item 27 above, wherein thesemiconductor substrate is heated at 800 to 900° C.

[0113] 33. A process as described under item 27 above, wherein selectiveoxidation of the principal surface of the semiconductor substrate iscarried out by single wafer-process system.

[0114] 34. A process as described under item 27 above, wherein selectiveoxidation of the principal surface of the semiconductor substrate iscarried out by batch treatment.

[0115] Effects available by the typical inventions, among the inventionsdisclosed by the present application, will next be described briefly.

[0116] According to the present invention, in gate processing using apoly-metal, oxidation of a metal film at the time of light oxidationtreatment subsequent to gate patterning can be prevented and at the sametime, the reproducibility of oxide film formation and homogeneity of anoxide film thickness at the side wall end portions of a gate can becontrolled favorably. In particular, an ultra-thin gate oxide film whichhas a film thickness not greater than 5 nm, has improved pressureresistance and has high quality can be formed with a uniform thicknessand good reproducibility, which brings about an improvement in thereliability and production yield of a device which has a circuit formedof a fine MOSFET having a gate length of 0.25 μm or less.

BRIEF DESCRIPTION OF THE DRAWINGS

[0117]FIG. 1 illustrates an equivalent circuit of DRAM according to oneembodiment of the present invention;

[0118]FIG. 2 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0119]FIG. 3 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0120]FIG. 4 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0121]FIG. 5 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0122]FIG. 6 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0123]FIG. 7 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0124]FIG. 8 is a fragmentary cross-sectional view of a semiconductorsubstrate which illustrates a fabrication process of DRAM according toone embodiment of the present invention;

[0125]FIG. 9(a) is a schematic plan view illustrating asingle-wafer-process type oxidizing furnace to be used for lightoxidation treatment and (b) is a cross-sectional view taken along a lineB-B′ of (a);

[0126]FIG. 10(a) is a schematic plan view illustrating asingle-wafer-process type oxidizing furnace to be used for lightoxidation treatment and (b) is a cross-sectional view taken along a lineB-B′ of (a);

[0127]FIG. 11 is a schematic view illustrating an apparatus forgenerating a water-vapor/hydrogen mixed gas by a catalytic system;

[0128]FIG. 12 is a graph illustrating temperature dependence of aequilibrium vapor pressure ratio in redox reaction using a watervapor/hydrogen mixed gas;

[0129]FIG. 13 illustrates a sequence of light oxidation process using asingle-wafer-process system;

[0130]FIG. 14 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0131]FIG. 15 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0132]FIG. 16 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0133]FIG. 17 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0134]FIG. 16 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0135]FIG. 19 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0136]FIG. 20 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0137]FIG. 21 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0138]FIG. 22 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0139]FIG. 23 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0140]FIG. 24 is a fragmentary cross-sectional view of a semiconductorsubstrate illustrating a fabrication process of DRAM according to oneembodiment of the present invention;

[0141]FIG. 25 is a schematic view of a batch-type vertical oxidizingfurnace to be used for light oxidation treatment; and

[0142]FIG. 26 illustrates a sequence of light oxidizing step using abatch-type vertical oxidizing furnace.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0143] The present invention will hereinafter be described morespecifically with reference to accompanying drawings. Incidentally, inall the drawings for illustrating embodiments, elements having likefunction will be identified by like reference numerals and overlappingdescriptions will be omitted.

[0144] The term “semiconductor integrated circuit device” as used hereinmeans any devices including not only those formed over a silicon waferbut also those formed over a substrate such as TFT liquid crystal unlessotherwise specifically indicated. Accordingly, the term “semiconductorwafer” means not only a silicon single-crystal wafer but also thosehaving a silicon epitaxial layer or the like formed over a siliconsingle-crystal substrate or insulator substrate.

[0145] In the below-described examples, same or similar descriptionswill not be repeated in principle unless otherwise particularlyrequired.

[0146] If necessary for convenience, the below-described examples willbe explained, divided into plural sections or plural examples. They,however, relate to each other and one section or example is amodification example, details or a complementary description of one orwhole portion of another section or example.

[0147] In the below-described examples, reference is made to the numberof elements (including the number, numerical value, quantity and range).The number of the elements, however, is not limited to a specific oneand elements may be used in the number less or greater than the specificnumber unless otherwise particularly indicated or apparently limited toa specific number in principle.

[0148] Furthermore in the below-described examples, it is obvious thatconstituting elements (including elemental steps or the like) are notalways indispensable unless otherwise particularly specified or unlessotherwise presumed to be apparently indispensable in principle.

[0149] Similarly, when reference is made to the shape, positionalrelationship or the like of constituting elements, those substantiallyclose or similar to their shapes or the like are included unlessotherwise specifically indicated or presumed to be apparently differentin principle. This also applies to the above-described numerical valueand range.

[0150]FIG. 1 illustrates an equivalent circuit of DRAM according to oneembodiment of the present invention. As illustrated, the memory array(MARY) of this DRAM is equipped with a plurality of word lines WL(WL_(n−1), WL_(n), WL_(n+1) . . .) and a plurality of bit lines BLdisposed in a matrix pattern, and a plurality of memory cells (MC)disposed at their intersections. One memory cell for the storage ofone-bit information is formed of one capacitative element C forinformation storage and one MISFETQs for memory cell selection connectedin series thereto. One of a source and drain of MISFETQs for memory cellselection is electrically connected with the capacitative element C forinformation storage and the other one is electrically connected with abit line BL. One end of a word line WL is connected with a word driverWD and one end of a bit line is connected with a sense amplifier SA.

[0151] A description will next be made of the fabrication process ofDRAM according to the embodiment of the present invention with referenceto FIGS. 2 to 24. Each of FIGS. 2 to 8 and FIGS. 14 to 24 is across-sectional view illustrating parts of memory array (MARY) andperipheral circuit (ex. sense amplifier SA); each of FIGS . 9 and 10 isa schematic view illustrating a single-wafer-process type oxidizingfurnace to be used for the light oxidation treatment;

[0152]FIG. 11 is a schematic view illustrating a water vapor/hydrogenmixed gas generating apparatus, which adopts a catalytic system,connected with a chamber of the single-wafer-process type oxidizingfurnace;

[0153]FIG. 12 is a graph illustrating temperature dependence of anequilibrium vapor pressure ratio of redox reaction using a watervapor/hydrogen mixed gas; and FIG. 13 illustrates a sequence of thelight oxidation process using a single-wafer-process type oxidizingfurnace. It should be borne in mind that the film thickness and the likeused in the below description will be offered by way of illustration butnot by way of limitation.

[0154] First, as illustrated in FIG. 2, a semiconductor substrate 1 madeof single crystal silicon having a specific resistance of about 10 Ωcmis heat treated to form a thin silicon oxide film 2 (pad oxide film)having a film thickness of about 10 nm over the principal surface of thesubstrate. Then, a silicon nitride film 3 having a film thickness ofabout 100 nm is deposited over the silicon oxide film 2 by the CVD(Chemical Vapor Deposition) method. The silicon nitride film 3 of anelement isolation region is removed by etching with a photoresist filmas a mask. The silicon oxide film 2 is formed in order to relax a stressto be added to the substrate when another silicon oxide film to beembedded inside of an element isolating groove is densified (sintered)later. The silicon nitride film 3 is resistant to oxidation so that itis used as a mask for preventing the oxidation of the surface of thesubstrate below the silicon nitride film (active region).

[0155] As illustrated in FIG. 3, the silicon oxide film 2 andsemiconductor substrate 1 are dry etched with the silicon nitride film 3as a mask, whereby a groove 4 a (element isolating groove) having adepth of about 300 to 400 nm is formed in an element isolating region ofthe semiconductor substrate 1.

[0156] As illustrated in FIG. 4, in order to remove a damage layerformed on an inside wall of the groove 4 a by the above-describedetching, the semiconductor substrate 1 is heat treated to form a siliconoxide film 5 having a film thickness of about 10 nm on the inside wallof the groove 4 a. Then, over the semiconductor substrate 1, a siliconoxide film 6 is deposited by the CVD method (embedded from outside withan embedding material. Instead of CVD, SOG or the like method can beemployed for the formation of an insulation film). For the improvementof the film quality of the silicon oxide film 6, the semiconductorsubstrate 1 is heat treated to densify (sinter) the silicon oxide film6. With the silicon nitride film 3 as a stopper, the silicon oxide film6 except the inside of the groove 4 a is polished by the chemicalmechanical polishing (CMP) method, whereby an element isolation groove 4is formed. (It is needless to say that the term “chemical mechanicalpolishing” as used herein means not only the polishing by suspendedabrasives but also mechanical flattening of the element formationsurface.)

[0157] In the next place, the silicon nitride film 3 remaining on thesemiconductor substrate 1 is removed by wet etching with hot phosphoricacid. Ions (boron) are then implanted to a region (memory array) inwhich a memory cell is to be formed and to a region (n-channel typeMISFETQn) in which a portion of a peripheral circuit is to be formed,each over the semiconductor substrate 1, whereby a p-type well 7 isformed. On the other hand, P (phosphorus) ions are implanted to a regionin which another portion of the peripheral circuit (p-channel typeMISFETQp) is to be formed, whereby an n-type well 8 is formed.

[0158] As illustrated in FIG. 6, the silicon oxide film 2 over thesurfaces of the p-type well 7 and n-type well 8 is removed using an HF(hydrofluoric acid) type detergent. Then, the semiconductor substrate 1is wet oxidized, whereby a clean gate oxide film 9 having a thickness of5 nm or so is formed over the surfaces of the p-type well 7 and n-typewell 8.

[0159] Although no particular limitation is imposed, oxidation andnitriding treatment for the segregation of nitrogen at the interfacebetween the gate oxide film 9 and semiconductor substrate 1 may becarried out after the formation of the gate oxide film 9 by thermallytreating the semiconductor substrate 1 in an NO (nitrogen oxide) or N₂O(dinitrogen monoxide) atmosphere. When the gate oxide film 9 becomes asthin as about 5 nm, distortion occurring at the interface due to thedifference in a thermal expansion coefficient between the gate oxidefilm 9 and the semiconductor substrate 1 becomes apparent, which inducesthe generation of hot carriers. Segregation of nitrogen at the interfacewith semiconductor substrate 1 relaxes the above distortion so that theabove oxidation and nitriding treatment brings about an improvement inthe reliability of the ultra-thin gate oxide film 9.

[0160] As illustrated in FIG. 7, a gate electrode 14A (word line WL) andgate electrodes 14B,14C, each having a gate length of about 0.25 μm, areformed over the gate oxide film 9. The gate electrode 14A (word line WL)and gate electrodes 14B,14C are formed by depositing by CVD, over thesemiconductor substrate 1, a polycrystalline silicon film 10 of about 70nm thick in which n-type impurities such as P (phosphorus) have beendoped, depositing thereon a WN film 11 of about 30 nm thick and a W film12 of about 100 nm thick by sputtering, depositing thereon a siliconnitride film 13 of about 150 nm thick and then patterning these filmswith a photoresist as a mask.

[0161] When a portion of the gate electrode 14A (word line WL) is formedof a low-resistance metal (W), its sheet resistance can be reduced evento 2 Ω/□, which makes it possible to reduce a word line delay. Inaddition, the delay of word line can be reduced without lining the gateelectrode 14 (word line WL) with an AL interconnection or the like sothat the number of the interconnection layers to be formed over thememory cell can be reduced by one.

[0162] Then, the photoresist is removed by ashing treatment, followed byremoval of the dry etching residue or ashing residue on thesemiconductor substrate 1 by an etching liquid such as hydrofluoricacid. By this wet etching, as illustrated in FIG. 8, the gate oxide film9 of the regions other than those below the gate electrode 14A (wordline WL) and not-illustrated gate electrodes 14B, 14C and also the gateoxide film 9 at the lower portions of the side walls of the gate areisotropically etched and undercuts appear, leading to an inconveniencesuch as lowering in the pressure resistance of the gate oxide film 9.Here, re-oxidation (light oxidation) treatment is carried out by thebelow-described process in order to regenerate the impaired gate oxidefilm 9.

[0163]FIG. 9(a) is a schematic plan view illustrating one example of aspecific constitution of a single-wafer-process type oxidizing furnaceto be used for the light oxidation treatment and FIG. 9(b) is across-sectional view taken along a line B-B′ of FIG. 9(a).

[0164] The single-wafer-process type oxidizing furnace 100 is equippedwith a chamber 101 made of a multiple-wall quartz tube, and above andbelow the chamber, heaters 102 a and 102 b are disposed for heating asemiconductor wafer 1A, respectively. Inside the chamber 101, housed isa disk-shaped soaking ring 103 for uniformly dispersing the heatsupplied from the heaters 102 a,102 b all over the semiconductor wafer1A and above the ring, a susceptor 104 for horizontally holding thesemiconductor wafer 1A is disposed. The soaking ring 103 is made of aheat-resistant material such as quartz or SiC (silicon carbide),and issupported by a supporting arm 105 which extends from the wall surface ofthe chamber 101. In the vicinity of the soaking ring 103 installed is athermocouple 106 for measuring the temperature of the semiconductorwafer 1A supported by the susceptor 104. For heating of thesemiconductor wafer 1A, heating system by a lamp 107 as illustrated inFIG. 10 may also be adopted as well as the heating system by heaters 102a, 102 b.

[0165] A portion of the side wall of the chamber 101 is connected withone end of a gas inlet tube 108 for introducing a water vapor/hydrogenmixed gas and purge gas into the chamber 101. The other end of this gasinlet tube 108 is connected with a catalytic system gas generator whichwill be described later. In the vicinity of the gas inlet tube 108, apartition 110 having many penetration holes 109 is disposed. The gasesintroduced into the chamber 101 passes through the penetration holes 109of this partition 110 and spreads uniformly inside of the chamber 101. Aportion of the opposite wall surface of the chamber 101 is connectedwith one end of an exhaust tube 111 for exhausting the above gasesintroduced into the chamber 101.

[0166]FIG. 11 is a schematic view illustrating a catalytic-system watervapor/hydrogen mixed gas generator connected with the chamber 101 of theabove single-wafer-process type oxidizing furnace 100. This gasgenerator 140 is equipped with a reactor 141 made of a heat- andcorrosion-resistant alloy (for example, Ni alloy known as “Hastelloy”,trade name) and has therein a coil 142 made of a catalytic metal such asPt (platinum), Ni (nickel) or Pd (palladium) and a heater 143 forheating the coil 142.

[0167] Into the reactor 141, a process gas made of hydrogen and oxygenand a purge gas made of an inert gas such as nitrogen or Ar (argon) areintroduced from gas reservoirs 144 a, 144 b, 144 c from a pipe 145.Between the gas reservoirs 144 a, 144 b and 144 c and the pipe 145,disposed) are mass flow controllers 146 a, 146 b and 146 c for adjustingthe amount of gases and switching valves 147 a, 147 b and 147 c foropening or closing the passage of the gases, respectively, by which theamount and component ratio of the gases introduced into the reactor 141are controlled precisely.

[0168] The process gas (hydrogen and oxygen) introduced into the reactor141 is excited, brought into contact with the coil 142 heated to about350 to 450° C., whereby a hydrogen radical is formed from a hydrogenmolecule (H₂→2H*) and an oxygen radical is formed from an oxygenmolecule (O₂→2O*). These two radicals are so chemically active that theyreact rapidly and form water (2H*+O*→H₂O). The introduction of a processgas containing more hydrogen than the molar ratio (hydrogen:oxygen=2:1)at which water (water vapor) is formed into the reactor 141 generates awater vapor/hydrogen mixed gas. The mixed gas so formed is introducedinto the chamber 101 of the single-wafer-process type oxidizing furnace100 through the gas inlet tube 108.

[0169] By the use of such a catalytic-system gas generator 140, theamount and ratio of hydrogen and oxygen which take part in the formationof water can be controlled with high precision, which makes it possibleto control the concentration of water vapor contained in the watervapor/hydrogen mixed gas introduced in the chamber 101 within a widerange from a markedly low concentration on the order of ppm to aconcentration as high as ten-odd %. Further, the water formation occursjust after the introduction of a process gas into the reactor 141 sothat a water vapor/hydrogen mixed gas having a desired concentration canbe obtained in real time. When the above generator is used, the mixingof foreign matters can be suppressed to the minimum so that a cleanwater vapor/hydrogen mixed gas can be introduced into the chamber 101.The catalyst metal in the reactor 141 is not limited to theabove-described metal insofar as it can convert hydrogen and oxygen intotheir radicals. In addition to the use of the catalyst metal in the coilform, it can be processed into a hollow tube or fine fiber filter,through which a process gas is allowed to pass.

[0170]FIG. 12 is a graph illustrating temperature dependence of anequilibrium vapor pressure ratio (P(H₂O)/P(H₂)) of redox reaction usinga water vapor/hydrogen mixed gas, in which curves (a) to (e) representequilibrium vapor pressure ratios of W, Mo, Ta (tantalum), Si and Ti,respectively.

[0171] As is illustrated, by setting the water vapor/hydrogen partialpressure ratio of the water vapor/hydrogen mixed gas to be introducedinto the chamber 101 of the single-wafer-process oxidizing furnace 100within a range of the region surrounded by the curves (a) and (d), onlySi can be selectively oxidized without oxidizing the W film 12 andbarrier WN film 11, which constitute a portion of the gate electrode 14A(word line WL) and gate electrodes 14B,14C. Furthermore, as illustrated,the lower the water vapor concentration in the water vapor/hydrogenmixed gas, the slower an oxidizing rate of any one of metals (W, Mo, Ta,Ti) and Si. It is therefore possible to control the oxidizing rate andoxide film thickness of Si easily by lowering the water vaporconcentration in the water vapor/hydrogen mixed gas.

[0172] Similarly, when a portion of the gate electrode is formed of anMo film, only Si can selectively be oxidized without oxidizing the Mofilm by setting the water vapor/hydrogen partial pressure ratio within arange of the region surrounded by the curves (b) and (d) When a portionof the gate electrode is formed by a Ta film, only Si can selectivelyoxidized without oxidizing the Ta film by setting the watervapor/hydrogen partial pressure ratio within a range of the regionsurrounded by curves (c) and (d).

[0173] As is illustrated, on the other hand, when a portion of the gateelectrode is formed of a Ti film or the barrier layer is formed of a TiNfilm, the selective oxidation of only Si cannot be attained withoutoxidizing the Ti film or TiN film because the oxidizing rate of Ti isgreater than that of Si in the water vapor/hydrogen mixed gasatmosphere. In this case, however, it is possible to suppressdeterioration of the properties of the gate electrode to a negligiblerange from the viewpoint of practical applications by setting theconcentration of water vapor in the water vapor/hydrogen mixed gas at alow concentration, thereby suppressing the oxidation of the Ti film orTiN film to the minimum. Described specifically, it is desired tosuppress the upper limit of the water vapor concentration to about 1% orless and to set the lower limit to about 10 ppm to 100 ppm because watervapor is required to some extent for improving the profile of theside-wall end portions of the gate electrode.

[0174] A description will next be made of one example of the sequence ofthe light oxidation process using the above-describedsingle-wafer-process oxidizing furnace 100, with reference to FIG. 13.

[0175] First, the chamber 101 of the single-wafer-process oxidizingfurnace 100 is opened and while a purge gas (nitrogen) is introducedinside of the chamber, the semiconductor wafer 1A is loaded on thesusceptor 104. The chamber 101 is then closed and gas exchange inside ofthe chamber 101 is carried out sufficiently by the continuousintroduction of the purge gas. The susceptor 104 is heated in advance bythe heaters 102 a and 102 b so that the semiconductor wafer 1A can beheated rapidly. The semiconductor wafer 1A is heated at a temperaturerange of from 800 to 900° C., for example, 850° C. Wafer temperatureslower than 800° C. deteriorate the quality of the silicon oxide film,while those higher than 900° C. tend to cause surface roughness of thewafer.

[0176] Next, hydrogen is introduced into the chamber 101, while nitrogenis discharged. It is desired to discharge nitrogen completely becausenitrogen remaining in the chamber 101 happens to cause undesirablenitriding reaction.

[0177] Then, oxygen and excess hydrogen are introduced into the reactor141 of the gas generator 140, followed by the introduction of watergenerated from oxygen and hydrogen by catalytic action into the chamber101 together with excess hydrogen, whereby the surface of thesemiconductor wafer 1A is oxidized for a predetermined time. By thisoxidation, the gate oxide film 9 which becomes thin by theabove-described wet etching can be oxidized again, which brings about animprovement in the profile of the undercut side-wall end portions of thegate electrode 14A (word line WL) and gate electrodes 14B,14C.

[0178] When the above-described light oxidation is effected for longhours, the oxide film thickness in the vicinity of the end portion ofthe gate electrode becomes unnecessarily thick, which causes offset atthe end portion of the gate electrode or deviation of the thresholdvoltage (Vth) of MOSFET from the designed value In addition, it issometimes accompanied with the problem that the effective channel lengthbecomes shorter than the processed value of the gate electrode. In aminute MOSFET having a gate length of about 0.25 μm, thinning tolerancefrom the designed value of gate processing size is severely limited fromthe viewpoint of the device design. This is because only a slightincrease in the thinning amount causes a drastic decrease in thethreshold voltage owing to short channel effects. In the case of a gateelectrode having a gate length of about 0.25 μm, an oxidized degree, inthe light oxidation process, of the side-wall end portion of apolycrystalline silicon film constituting a part of the gate electrodein an amount of about 0.1 μm (about 0.2 μm in total of both endportions) is presumed to be a limitation which does not cause a drasticdecrease in the threshold voltage. Accordingly, it is desired to set theupper limit of the oxide film thickness grown by light oxidation is anabout 50% increase of the gate oxide film thickness.

[0179] After the water vapor/hydrogen mixed gas is discharged byintroducing a purge gas (nitrogen) into the chamber 101, the chamber 101is opened. While a purge gas is introduced inside of the chamber 101,the semiconductor wafer 1A is unloaded from the susceptor 104, wherebythe light oxidation treatment is completed.

[0180] Next, the DRAM process subsequent to the light oxidation processwill be described simply. First, as illustrated in FIG. 14, p-typeimpurities such as B (boron) are ion-implanted to the n-type well 8,whereby p-type semiconductor regions 16 are formed in the n-type well 8on both sides of the gate electrode 14C. On the other hand, n-typeimpurities such as p (phosphorus) are ion-implanted to the p-type well7, whereby n-type semiconductor regions 17 are formed in the p-type well7 on both sides of the gate electrode 14B and n-type semiconductorregions 18 are formed in the p-type well 7 on both sides of the gateelectrode 14A.

[0181] As illustrated in FIG. 15, a silicon nitride film 19 is depositedover the semiconductor substrate 1 by the CVD method. As illustrated inFIG. 16, the memory array is then covered with a photoresist film 20 andby anisotropic etching of the silicon nitride film 19 of the peripheralcircuit, side wall spacers 19 a are formed on the side walls of the gateelectrodes 14B,14C. Upon this anisotropic etching, the overetchingamount is suppressed to the minimum and at the same time, an etching gaswhich permits a large selection ratio to the silicon oxide film 6 isemployed, for the purpose of suppressing the cut amount of the siliconoxide film 6 embedded in the element separating groove 4 and that of thesilicon nitride film 19 over the gate electrodes 14B and 14C to theminimum.

[0182] As illustrated in FIG. 17, n-type impurities, for example, As(arsenic) are ion-implanted to the p-type well 7 of the peripheralcircuit, whereby an n+ type semiconductor region 21 (source, drain) ofn-channel type MISFETQn is formed. On the other hand, p-type impurities,for example, B (boron) are ion-implanted to the n-type well 2, whereby ap+ type semiconductor region 22 (source, drain) of p-channel typeMISFETQp is formed.

[0183] As illustrated in FIG. 18, a silicon oxide film 23 is depositedover the semiconductor substrate 1 by the CVD method, followed byflattening of the surface by the chemical mechanical polishing method.The silicon oxide film 23 over the n-type semiconductor regions 18(source, drain) of MISFETQs for memory cell selection is then removed bydry etching with a photoresist film 24 as a mask. This etching iscarried out under the conditions such that the etching rate of thesilicon oxide film 23 becomes greater than that of the silicon nitridefilms 13,19, whereby the removal of the silicon nitride film 19 over then-type semiconductor region 18 can be prevented.

[0184] As illustrated in FIG. 19, the silicon nitride film 19 and thegate oxide film 9 over the n-type semiconductor regions 18 (source,drain) of MISFETQs for memory cell selection are removed by dry etchingwith the above photoresist film 24 as a mask, whereby a contact hole 25is formed over one of the source and drain (n-type semiconductor region18) and a contact hole 26 is formed over the other one of the source anddrain (n-type semiconductor region 18). In order to suppress the cutamount of the semiconductor substrate 1, this dry etching is carried outby suppressing the over etching amount to the minimum level and using anetching gas which permits a large selection ratio to the semiconductorsubstrate 1 (silicon). Furthermore, this etching is carried out underthe conditions permitting the anisotropic etching of the silicon nitridefilm 19, thereby allowing the silicon nitride film 19 to remain on theside walls of the gate electrode 14A (word line WL). In this manner,contact holes 25 and 26 are formed in self alignment with the gateelectrode 14A (word line WL). It is also possible to form side wallspacers in advance on the side walls of the gate electrode 14A (wordline WL) by anisotropic etching of the silicon nitride film 19 in orderto form the contact holes 25,26 in self alignment with the gateelectrode 14A (word line WL).

[0185] As illustrated in FIG. 20, plugs 27 are embedded inside of thecontact holes 25 and 26, followed by deposition of a silicon oxide film28 over the silicon oxide film 23 by the CVD method. Then, the siliconoxide film 28 over the contact hole 25 is removed by dry etching with aphotoresist film 29 as a mask. The plugs 27 are embedded inside of thecontact holes 25 and 26 by depositing, over the silicon oxide film 23, apolycrystalline silicon film having P (phosphorus) doped therein, andthen polishing the resulting polycrystalline silicon film by chemicalmechanical polishing method to remove the polycrystalline silicon filmover the silicon oxide film 23. A portion of P (phosphorus) in thepolycrystalline silicon film diffuses from the bottom of the contactholes 25,26 to the n-type semiconductor regions 18 (source, drain) uponthe high-temperature step which will be conducted later, therebylowering the resistance of the n-type semiconductor regions 18.

[0186] As illustrated in FIG. 21, the silicon oxide films 28 and 23 andgate oxide film 9 of the peripheral circuit are removed by dry etchingwith a photoresist 30 as a mask, whereby contact holes 31 and 32 areformed over the source and drain (n+ type semiconductor regions 21) ofthe n-channel type MISFETQn and contact holes 33 and 34 are formed overthe source and drain (P+ type semiconductor regions 22) of the p-channeltype MISFETQp. This etching is carried out in such a way that theetching rate of the silicon oxide film becomes larger relative to thesilicon nitride film 13 and sidewall spacer 19 a. The contact holes 31and 32 are formed in self alignment with the gate electrode 14B, whilethe contact holes 33 and 34 are formed in self alignment with the gateelectrode 14C.

[0187] As illustrated in FIG. 22, a bit line BL and the first filminterconnections 35 and 36 of the peripheral circuit are formed over thesilicon oxide film 28. The bit line BL and first film interconnections35 and 36 are formed, for example, by depositing a TiN film and a W filmover the silicon oxide film 28 by sputtering, depositing a silicon oxidefilm 37 over the W film by the CVD method and then patterning thesefilms successively by using a photoresist film as a mask.

[0188] As illustrated in FIG. 23, a silicon oxide film 38 is depositedover the bit line BL and the first film interconnections 35 and 36 bythe CVD method. With a photoresist film as a mask, the silicon oxidefilms 38 and 28 over the contact hole 26 are removed by dry etching,whereby a through hole 39 is formed. A plug 40 is embedded inside ofthis though hole 39. The plug 40 is formed, for example, by depositing aW film over the silicon oxide film 38 by sputtering and then polishingthe resulting W film by chemical and mechanical polishing method so asto leave the W film inside of the through hole 39.

[0189] As illustrated in FIG. 24, a capacitative element C for theinformation storage which is made of a lower electrode 41, capacitativeinsulating film 42 and upper electrode 43 stacked one after another, isformed over the through hole 39, whereby a memory cell of DRAM havingMISFETQs for memory cell selection and the capacitative element C forinformation storage connected in series therewith is substantiallycompleted. The lower electrode 41 of the capacitative element C forinformation storage is formed, for example, by depositing a W film overthe silicon oxide film 38 by the CVD or sputtering method and thenpatterning the resulting W film by dry etching with a photoresist filmas a mask. The capacitative insulation film 42 and the upper electrode43 are formed by depositing a tantalum oxide film over the lowerelectrode 41 by the CVD or sputtering method, depositing thereon a TiNfilm by sputtering and then patterning these films successively byetching with a photoresist film as a mask. Over the capacitative elementC for information storage, an A1 interconnection made of two films or sois formed but it is not illustrated.

[0190] The light oxidation treatment of the gate oxide film can also becarried out by installing a catalytic system water vapor/hydrogen mixedgas generator 140 as described above to a batch system verticaloxidizing furnace 150 as illustrated in FIG. 25. FIG. 26 illustrates oneexample of the sequence of the light oxidation treatment step by usingthe batch system vertical oxidizing furnace 150.

[0191] The invention completed by the present inventors was specificallydescribed above based on its embodiments. It should be borne in mind,however, that the present invention is not limited to these embodimentsbut can be modified within a range not departing from its spirit orscope of the present invention as set forth herein.

[0192] In the above embodiment, a description was made of the lightoxidation treatment of MOSFET which constitutes a memory cell and aperipheral circuit of DRAM. The present invention is not limited theretobut is particularly suited for use in the light oxidation treatment ofvarious devices having a circuit formed of a minute MOSFET which isrequired to have a gate oxide film of a thickness as thin as 5 nm orless formed uniformly and with good reproducibility.

What is claimed is:
 1. A process for the fabrication of a semiconductorintegrated circuit device, comprising the steps of: (a) forming asilicon film over a silicon-oxide-film-containing gate insulation filmwhich has been formed over a silicon surface of a wafer; (b) forming arefractory metal film of tungsten or molybdenum over said silicon filmthrough a medium of a barrier layer of a nitride of tungsten; (c)forming a gate electrode by patterning said silicon film and saidrefractory metal film; and (d) after said step (c), thermally oxidizingthe silicon film without oxidizing said refractory metal film, under agas ambient containing (1) hydrogen, and (2) water vapor synthesizedfrom a mixed gas of oxygen and hydrogen gases by a catalyst, andcontaining substantially no hydrogen radicals, the partial pressure ofthe water vapor being lower than that of the hydrogen in the gasambient.
 2. A process according to claim 1 , wherein said gas ambientdoes not contain nitrogen gas.
 3. A process according to claim 1 ,wherein in the step (d), said wafer is heated to a temperature in arange of 800 to 900° C.
 4. A process for the fabrication of asemiconductor integrated circuit device, comprising the steps of: (a)forming a silicon film over a silicon-oxide-film-containing gateinsulation film, the gate insulation film having a thickness of not morethan 5 nm and being formed over a silicon surface of a major surface ofa wafer; (b) forming a refractory metal film over said silicon film; (c)forming a gate electrode by patterning said silicon film and saidrefractory metal film, a gate length of the gate electrode being notmore than 0.25 μm; and (d) after said step (c), thermally oxidizing thesilicon film without oxidizing said refractory metal film, under ahydrogen gas ambient containing water vapor synthesized from a mixed gasof oxygen and hydrogen gases by a catalyst, the partial pressure of thewater vapor being lower than that of the hydrogen in the hydrogen gasambient, the upper limit of total oxide film thickness grown by saidthermally oxidizing being about one and a half of the thickness of thegate insulation film.
 5. A process according to claim 4 , wherein saidhydrogen gas ambient does not contain nitrogen.
 6. A process accordingto claim 4 , wherein in step (d), said wafer is heated to a temperaturein a range of 800 to 900° C.
 7. A process for the fabrication of asemiconductor integrated circuit device, comprising the steps of: (a)forming a first film of silicon over a silicon-oxide-film-containinggate insulation film which has been formed over a silicon surface of amajor surface of a wafer; (b) forming a refractory metal film oftungsten or molybdenum over said first film; (c) forming a gateelectrode by patterning said first film and said refractory metal film;and (d) after said step (c), thermally oxidizing the first film withoutoxidizing said refractory metal film, under a hydrogen gas ambient,substantially without nitrogen gas, the hydrogen gas ambient containingwater vapor synthesized from a mixed gas of oxygen and hydrogen gases bya catalyst, the partial pressure of the water vapor being lower thanthat of hydrogen gas in the hydrogen gas ambient.
 8. A process for thefabrication of a semiconductor integrated circuit device, comprising thesteps of: (a) forming an isolation groove in a silicon surface of amajor surface of a wafer; (b) embedding an insulating material in saidgroove; (c) after the step (b), planarizing the major surface of saidwafer by chemical mechanical polishing; (d) forming a silicon film overa gate insulation film containing a silicon oxide film having athickness not more than 5 nm, said silicon oxide film being a principalportion of the entire thickness of the gate insulation film, the siliconoxide film having been formed over the silicon surface of said wafer bythermally oxidizing the silicon surface; (e) forming a refractory metalfilm over said silicon film; (f) forming a gate electrode by patterningsaid silicon film and said refractory metal film, the gate length ofsaid gate electrode being not more than 0.25 μm; and (g) after said step(f), thermally oxidizing the silicon film without oxidizing saidrefractory metal film, under a hydrogen gas ambient containing watervapor, the partial pressure of the water vapor being lower than that ofthe hydrogen in the hydrogen gas ambient.
 9. A process according toclaim 8 , wherein said hydrogen gas ambient does not contain nitrogengas.
 10. A process according to claim 8 , wherein in step (g), saidwafer is heated to a temperature in a range of 800 to 900° C.
 11. Aprocess for the fabrication of a semiconductor integrated circuitdevice, comprising the steps of: (a) forming a silicon film over asilicon-oxide-film-containing gate insulation film, the gate insulationfilm having a thickness not more than 5 nm and formed over a siliconsurface of a major surface of a wafer; (b) forming a refractory metalfilm of tungsten over said silicon film; (c) forming a gate electrode bypatterning said silicon film and said refractory metal film, the gatelength of said gate electrode being not more than 0.25 μm; and (d) aftersaid step (c), thermally oxidizing the silicon film without oxidizingsaid refractory metal film, under a gas ambient containing hydrogen andwater vapor, and containing substantially no hydrogen radicals, thepartial pressure of the water vapor being lower than that of thehydrogen in the gas ambient.
 12. A process for the fabrication of asemiconductor integrated circuit device, comprising the steps of: (a)forming a refractory metal film of tungsten of molybdenum over asilicon-oxide-film-containing gate insulation film, the gate insulationfilm having a thickness not more than 5 nm and having been formed over asilicon surface of a major surface of a wafer; (b) forming a gateelectrode by patterning said refractory metal film, the gate length ofsaid gate electrode being not longer than 0.25 μm; and (c) after saidstep (b), thermally oxidizing the silicon surface without oxidizing saidrefractory metal film, under a hydrogen gas ambient containing watervapor synthesized from a mixed gas of oxygen and hydrogen gases by acatalyst, and containing substantially no hydrogen radicals, the partialpressure of the water vapor being lower than that of the hydrogen in thehydrogen gas ambient.
 13. A process for the fabrication of asemiconductor integrated circuit device, comprising the steps of: (a)forming a refractory metal film of tungsten or molybdenum over asilicon-oxide-film-containing gate insulation film, the gate insulationfilm having a thickness not more than 5 nm and having been formed over asilicon surface of a major surface of a wafer; (b) forming a gateelectrode by patterning said refractory metal film, the gate length ofsaid gate electrode being not longer than 0.25 μm; and (c) after saidstep (b), thermally oxidizing the silicon surface without oxidizing saidrefractory metal film, under a hydrogen gas ambient, substantiallywithout nitrogen gas, the hydrogen gas ambient containing water vaporsynthesized from a mixed gas of oxygen and hydrogen gases by a catalyst,and containing substantially no hydrogen radicals, the partial pressureof the water vapor being lower than that of the hydrogen in the hydrogengas ambient, the thermal oxidation of the silicon surface beingperformed at a temperature such that, in the hydrogen gas ambient,titanium nitride would be oxidized and a nitride of tungsten would notbe oxidized.
 14. A process according to claim 13 , wherein in step (c),the wafer is heated to a temperature in a range of 800 to 900° C.
 15. Aprocess for the fabrication of a semiconductor integrated circuitdevice, comprising the steps of: (a) forming an isolation groove in asilicon surface of a major surface of a wafer; (b) embedding aninsulating material in said groove; (c) after said step (b), planarizingsaid major surface of said wafer by chemical mechanical polishing; (d)forming a refractory metal film over a gate insulation film containing asilicon oxide film, having a thickness not more than 5 nm, as aprincipal portion of the entire thickness of the gate insulation film,said silicon oxide film having been formed over the silicon surface ofsaid wafer by thermally oxidizing the silicon surface; (e) forming agate electrode by patterning said refractory metal film, the gate lengthof said gate electrode being not longer than 0.25 μm; and (f) after saidstep (e), thermally oxidizing the silicon surface without oxidizing saidrefractory metal film, under a hydrogen gas ambient containing watervapor, the partial pressure of the water vapor being lower than that ofthe hydrogen in the hydrogen gas ambient.
 16. A process according toclaim 15 , wherein said hydrogen gas ambient does not contain nitrogengas.
 17. A process according to claim 15 , wherein in the step (f), saidwafer is heated to a temperature in a range of 800 to 900° C.
 18. Aprocess for the fabrication of a semiconductor integrated circuitdevice, the semiconductor integrated circuit device comprising: (a) agate insulating film over a silicon-base surface region; (b) a gateelectrode having: (i) a lower polysilicon film constituting asilicon-base region together with the silicon-base surface region, saidsilicon-base region including silicon as its principal component; and(ii) an upper refractory metal film including a refractory metal as itsprincipal component, wherein the upper refractory metal film constitutesa refractory metal region including a refractory metal as one of itsprincipal components, and the gate insulating film and the gateelectrode are elements of an insulated gate field effect transistor overa major surface of a substrate region, the fabrication processcomprising: (x) after patterning the gate electrode, performing heattreatment, in a heat treatment chamber of a single wafer processingfurnace by lamp heating under a mixed gas ambient including hydrogen gasand water vapor synthesized from hydrogen gas and oxygen gas bycatalyst, of a wafer including the substrate region so as to oxidize thesilicon-base region without oxidizing the refractory metal region.
 19. Aprocess according to claim 18 , wherein said water vapor synthesizedfrom hydrogen gas and oxygen gas is transferred into the heat treatmentchamber while maintaining its gas state.
 20. A process according toclaim 19 , wherein said synthesis of water vapor is performed at atemperature lower than that of the heat treatment of the wafer.
 21. Aprocess according to claim 20 , wherein a gate length of the insulatedgate field effect transistor is not longer than 0.25 μm.
 22. A processaccording to claim 21 , wherein a thickness of the gate insulating filmis not thicker than 5 nm.
 23. A process according to claim 22 , whereinthe composition of hydrogen and oxygen in a gas provided to synthesizethe r vapor is hydrogen-rich.
 24. A process according to claim 23 ,wherein the heat treatment is performed at a temperature not lower than800 degrees centigrade.
 25. A process for the fabrication of asemiconductor integrated circuit device, comprising: (a) forming a firstinsulating film over a surface region, said surface region includingsilicon as its principal component, over a major surface of a wafer,wherein said first insulating film is to be a gate insulating film of aninsulated gate field effect transistor; (b) forming a firstsilicon-containing film over the first insulating film, wherein saidfirst silicon-containing film includes silicon as its principalcomponent; (c) forming a first refractory metal film over the firstsilicon containing film, wherein said first refractory metal filmincludes refractory metal as its principal component; (d) forming a gateelectrode of the insulated gate field effect transistor by patterningthe first silicon-containing film and the first refractory metal film;(e) after step (d), performing heat treatment, in a heat treatmentchamber of a single wafer processing furnace by lamp heating under amixed gas ambient including hydrogen gas and water vapor synthesizedfrom hydrogen gas and oxygen gas by catalyst, of the wafer so as tooxidize the surface region and the first silicon-containing film withoutoxidizing the first refractory metal film.
 26. A process according toclaim 25 , wherein said water vapor synthesized from hydrogen gas andoxygen gas is transferred into the heat treatment chamber whilemaintaining its gas state.
 27. A process according to claim 26 , whereinthe synthesis of water vapor is performed at a temperature lower thanthat of the heat treatment of the wafer.
 28. A process according toclaim 27 , wherein a gate length of the gate electrode of the insulatedgate field effect transistor is not longer than 0.25 μm.
 29. A processaccording to claim 28 , wherein a thickness of the gate insulating filmis not thicker than 5 nm.
 30. A process according to claim 29 , whereinthe composition of hydrogen and oxygen in a gas provided to synthesizethe water vapor is hydrogen-rich.
 31. A process according to claim 30 ,wherein the heat treatment of the wafer is performed at a temperaturenot lower than 800 degrees centigrade.
 32. A process for the fabricationof a semiconductor integrated circuit device, comprising: (a) forming afirst insulating film over a silicon surface region over a major surfaceof a wafer, wherein said first insulating film is to be a gateinsulating film of an insulated gate field effect transistor; (b)forming a first silicon-containing film over the first insulating film,wherein said first silicon-containing film includes silicon as itsprincipal component; (c) forming a first refractory metal film over thefirst silicon-containing film; (d) forming a gate electrode of theinsulated gate field effect transistor by patterning the firstsilicon-containing film and the first refractory metal film; (e) afterstep (d), performing heat treatment, in a heat treatment chamber of asingle wafer processing furnace by lamp heating under a mixed gasambient including hydrogen gas and water vapor synthesized from hydrogengas and oxygen gas by catalyst, of the wafer so as to oxidize thesurface region and the first silicon-containing film without oxidizingthe first refractory metal film.
 33. A process according to claim 32 ,wherein said water vapor synthesized from hydrogen gas and oxygen gas istransferred into the heat treatment chamber while maintaining its gasstate.
 34. A process according to claim 33 , wherein the synthesis ofwater vapor is performed at a temperature lower than that of the heattreatment of the wafer.
 35. A process according to claim 34 , wherein agate length of the gate electrode of the insulated gate field effecttransistor is not longer than 0.25 μm.
 36. A process according to claim35 , wherein a thickness of the gate insulating film is not thicker than5 nm.
 37. A process according to claim 36 , wherein the composition ofhydrogen and oxygen in a gas provided to synthesize the water vapor ishydrogen-rich.
 38. A process according to claim 37 , wherein the heattreatment of the wafer is performed at a temperature not lower than 800degrees centigrade.